ReaxFF molecular dynamics simulations of the initial pyrolysis mechanism of unsaturated triglyceride

ZQ Zhang and KF Yan and JL Zhang, JOURNAL OF MOLECULAR MODELING, 20, 2127 (2014).

DOI: 10.1007/s00894-014-2127-6

To understand the impact of C=C double bonds in acyl chains of unsaturated triglycerides on the reaction mechanism and product composition in their initial pyrolysis process, ReaxFF molecular dynamics simulations were carried out using a molecular model, trilinolenin, at temperatures of 2000, 2250, and 2500 K. Analyses indicated that the observed pyrolysis mechanisms of unsaturated triglyceride are nearly identical to the saturated triglyceride, and the pyrolysis products also include alkanes, alkenes, alkadienes, aromatics, oxygenated species, CO2, and H-2. The formation of intermediates and products is a sequential process. Three C-O bonds in trilinolenin molecule are usually successive dissociated first, leading to the formation of unsaturated C3H5 center dot radical and straight-chain C18H29O2 center dot (RCOO) radicals. Following that, the deoxygenated alkenyl chain is produced through decarboxylation of RCOO.radicals with consequent release of CO2. The resulting hydrocarbon radicals undergo a variety of disproportionation, isomerization, and hydrogen-transfer reactions, yielding straight and branched-chain hydrocarbons. It was found that the scission of C-O bond and decarboxylation should preferentially occur before the cleavage of the C-C bond beta to the C=C bond in the initial decomposition process of unsaturated trilinolenin. In addition, the formation of cyclic hydrocarbons could proceed through intramolecular cyclization mechanisms, including non-radical electrocyclic, biradical cyclization and cyclization of alkenyl radical, which are inconsistent with previously proposed bimolecular Diels-Alder addition mechanisms. More rapid pyrolysis of trilinolenin would occur at higher temperatures without significantly affecting the apparent reaction mechanisms of trilinolenin pyrolysis in the considered temperature range. Aromatic ring structures are observed to be stable after formation and do not decay within the 500 ps simulation period.

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